CN103088323B - Method for preparing Ni-P-CNT (Carbon nanotube) nano composite coating - Google Patents
Method for preparing Ni-P-CNT (Carbon nanotube) nano composite coating Download PDFInfo
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Abstract
The invention discloses a method for preparing a Ni-P-CNT (Carbon nanotube) nano composite coating. The method comprises the following steps of: performing acid oxidation treatment on a carbon nano-tube (CNT) before coating, utilizing an ultrasonic dispersion technology and adding a proper amount of surfactant into a chemical plating solution, so that the CNT is uniformly dispersed in the chemical plating solution. A proper chemical plating solution formula is selected, a proper amount of surfactant is added, the coating solution is not decomposed and precipitated in the chemical plating process through an intermittent magnetic stirring method, the chemical and physical characteristics are stable and reliable, the nano composite coating which is high in hardness, wear resistance and corrosion resistance is prepared compared with the traditional Ni-P coating, and the problem that the CNT is dispersed is solved.
Description
Technical field
The invention belongs to electroless plating Application Areas, relate to a kind of preparation method of new Ni-P-CNT nano-composite coating, be mainly used in wear-resisting, corrosion-resistant functional coating and the decorative coveringn of various metal species component and material.
Background technology
Nano surface work is based on nano material and the non-equilibrium material of other low fibers, by specific processing technology and means, strengthens solid surface, modification, hyperfine processing or give the systems engineering of surperficial New function.In brief, nano surface work be exactly nano material and nanotechnology are intersected with Surface Engineering, compound, comprehensive and Application and Development.
Adopt the method for electroless plating, in common plating solution, add nanoparticle, make nanoparticle and matrix metal codeposition under whipped state and the composite deposite that obtains is called nano-composite coating.These nano particles have SiC, SiO usually
2, Al
2o
3and the nano particle such as diamond.The research of nano-composite coating starts from the nineties in 20th century, has become the focus of Composite Plating at present, is a kind of important means preparing nano material.
The surfactivity that nanoparticle is high makes it very easily exist with aggregating state, and the nanoparticle of reunion state often also will lose its distinctive physics and chemical property.Thus one of gordian technique preparing nano-composite coating, to be how to solve in plating solution and the agglomeration traits of nanoparticle in the nano-composite coating formed subsequently, this is also one of maximum difference of it and conventional Composite Plating, and research nano particle in the plating solution dispersed and stable suspersion is basis and the key of preparing high-performance nano compound coating.
At present, the research of micron composite deposite has the history of decades, and oneself prepares the coating of various excellent performance, obtains apply widely in fields such as Aeronautics and Astronautics, automobile, electronics.Be applied in by nano particle to obtaining the nano-composite coating than the hardness, wear resistance, antifriction quality, solidity to corrosion etc. of common Composite Coatings floor height in plating, electroless plating and Brush Plating, oneself is through obtaining larger progress in recent years, but still is in the exploratory stage.At present, there is following problem:
(1) in nano-composite coating, the co-deposition mechanism of nano particle and metal ion there is no perfect theoretical explanation;
(2) bath stability sex chromosome mosaicism.Because nano particle itself exists certain catalytic performance, more easily bring out the decomposition of plating solution, add stablizer and be adsorbed on active material surface, the life cycle of plating solution can be made to extend;
(3) scattering problem of nano particle in composite plating bath and composite deposite.The method solving nanoparticle agglomerates has mechanical stirring, magnetic agitation, gas stirring and ultrasonic wave to disperse usually, and the most effective way adds tensio-active agent at present, but its dispersion problem is well solved not yet;
(4) performance of nano-composite coating really increases compared with micron composite deposite, but whether can reach best performance and depend on the factors such as the dispersiveness of nano particle and plating technology completely.
Summary of the invention
The defect existed for above-mentioned prior art or deficiency, the object of the invention is to, and provides a kind of preparation method of Ni-P-CNT nano-composite coating, and the Ni-P-CNT nano-composite coating prepared by the method, CNT nano particle is dispersed in composite deposite.
In order to realize above-mentioned task, the present invention is achieved by the following technical solutions:
A preparation method for Ni-P-CNT compound coating, is characterized in that, concrete preparation process is as follows:
Step one, carries out pre-grinding process by matrix, makes any surface finish;
Step 2, is placed in alkaline wash by the matrix after pre-grinding process, and soak 10min, temperature is 80 DEG C, and described alkaline wash is by sodium hydroxide: 50g/L, sodium carbonate: 5g/L, tertiary sodium phosphate: 25g/L, the aqueous solution that water glass 13g/L is formulated;
Step 3, is placed in pickle solution by the matrix after alkali cleaning and soaks 5min, with distilled water flushing after pickling, described pickle solution to be concentration be 10% sulphuric acid soln;
Step 4, is placed in activation solution by matrix through the matrix of overpickling and activates 30s, described activation solution to be concentration be 4% hydrochloric acid soln;
Step 5, carbon nanotube is carried out acid oxidase process, the method of described acid oxidase process is: the vitriol oil and the concentrated nitric acid that carbon nanometer tube material are placed in volume fraction 3:1 boil 6h, are finally washed till neutrality with deionized water, puts into loft drier and carry out drying after filtration at 80 DEG C;
Step 6, preparation chemical plating solution, described chemical plating solution is by single nickel salt: 28g/L, inferior sodium phosphate: 30g/L, anhydrous sodium acetate: 16g/L, Trisodium Citrate: 16g/L, carbon nanotube: 0.1g/L ~ 0.5g/L, tensio-active agent: 0.4g/L, thiocarbamide: 1g/L, with the aqueous solution of lactic acid adjust ph 6 ~ 8;
Step 7, carries out magnetic agitation by the chemical plating solution configured; And in chemical plating solution, add the tensio-active agent of 0.3g/L; And carry out ultrasonic oscillation;
Step 8, is placed in chemical plating solution by the matrix through overactivation, magnetic force intermittent stirring, and under temperature is 88 DEG C of conditions, plating 1.5h, namely obtains Ni-P-CNT compound coating on matrix surface.
Adopt the preparation method of Ni-P-CNT nano-composite coating of the present invention, the CNT length in chemical plating solution shortens, and reunite and obviously reduce, and the suspended dispersed of CNT is significantly improved.The Ni-P-CNT nano-composite coating adopting the method to obtain has higher CNT content, and coatingsurface is relatively uniform smooth, and performance is more superior.
At present, along with the progress and development of science and technology, the demand of people to high performance material constantly increases, many work condition environments require component of machine and material should wear resistant friction reducing corrosion-resistant again.Because carbon nanotube (Carbon nano-tube, CNT) has excellent mechanical property, high chemical stability and good toughness, also there is good self lubricity, and Electroless Ni-P Coating has extraordinary corrosion resistance nature simultaneously.Therefore, the present invention is using CNT as the reinforcement of nickel-phosphorus composite deposit, and wear resistant friction reducing, the corrosion-resistant and self-lubricating property of the Ni-P-CNT nano-composite coating tool excellence of acquisition, can meet the needs of practical implementation.
Accompanying drawing explanation
Fig. 1 is preparation technology's schema of Ni-P-CNT nano-composite coating of the present invention;
Fig. 2 is carbon nanotube TEM photo before and after acid treatment; Wherein scheming (a) and scheming (b) is the carbon nanotube TEM photo before acid treatment, and figure (c) and figure (d) is the carbon nanotube TEM photo after acid treatment;
Fig. 3 is carbon nanotube infrared spectrogram sheet before and after acid treatment;
Fig. 4 is CNT content histogram in the Ni-P-CNT nano-composite coating of embodiment 11, embodiment 12, embodiment 13 and embodiment 14 acquisition;
Fig. 5 is the Ni-P-CNT nano-composite coating surface topography (200 times of metallographs) that embodiment 11, embodiment 12, embodiment 13 and embodiment 14 obtain, wherein, figure (a): surfactant-free, figure (b): add Surfactant SDS (SDS), figure (c): add tensio-active agent cetyl trimethylammonium bromide (CTAB), figure (d): add surfactant polyethylene (PEG);
Fig. 6 is the Ni-P-CNT nano-composite coating surface topography SEM photo that enforcement 12 obtains, and wherein scheming (a) is 5000 times of mirror images, and figure (b) is 100000 times of mirror images;
Fig. 7 is the Ni-P-CNT nano-composite coating Cross Section Morphology SEM photo that enforcement 12 obtains;
Fig. 8 is the energy spectrogram of the Ni-P-CNT nano-composite coating that embodiment 12 obtains;
Fig. 9 is the Ni-P-CNT nano-composite coating hardness histogram that embodiment 11, embodiment 12, embodiment 13 and embodiment 14 obtain;
Figure 10 is the Ni-P-CNT nano-composite coating polarization curve that embodiment 11, embodiment 12, embodiment 13 and embodiment 14 obtain;
Figure 11 is the surface topography (100 times of metallographs) of the Ni-P-CNT nano-composite coating that embodiment 12, embodiment 15, embodiment 16, embodiment 17, embodiment 18 and embodiment 19 obtain;
Figure 12 is the Ni-P-CNT nano-composite coating polarization curve that embodiment 12, embodiment 15, embodiment 16, embodiment 17, embodiment 18 and embodiment 19 obtain;
Figure 13 is the Ni-P-CNT nano-composite coating wear rate broken line that embodiment 12, embodiment 15, embodiment 16, embodiment 17, embodiment 18 and embodiment 19 obtain;
Figure 14 is the Ni-P-CNT nano-composite coating friction coefficient curve that embodiment 12, embodiment 15, embodiment 16, embodiment 17, embodiment 18 and embodiment 19 obtain;
Figure 15 is the Ni-P-CNT nano-composite coating abrasion pattern (50 times of metallographs) that embodiment 12, embodiment 15, embodiment 16, embodiment 17, embodiment 18 and embodiment 19 obtain;
Figure 16 is the wear rate curve of Ni-P-CNT nano-composite coating when load is 10N that embodiment 12, embodiment 15 and embodiment 20 obtain;
Figure 17 is the wear morphology of Ni-P-CNT nano-composite coating when load is 10N (50 times, 200 times metallographs) that embodiment 12, embodiment 15 and embodiment 20 obtain.
Embodiment
Below in conjunction with specific embodiment, the present invention is more specifically described in detail.
Be below the embodiment that contriver provides, below in an example, matrix adopts 45# steel, the invention is not restricted to these embodiments, as long as body material conducts electricity.
Below in an example, acid oxidase solution used, alkaline wash, pickle solution, activation solution, chemical plating solution are as follows respectively:
1) acid oxidase solution: be the vitriol oil of volume fraction 3:1 and the mixing solutions of concentrated nitric acid.
2) alkaline wash is by sodium hydroxide: 50g/L, sodium carbonate: 5g/L, tertiary sodium phosphate: 25g/L, the aqueous solution that water glass 13g/L is formulated.
3) pickle solution: to be concentration be 10% sulphuric acid soln.
4) activation solution: to be concentration be 4% hydrochloric acid soln.
5) chemical plating solution is the aqueous solution containing following component: single nickel salt: 28g/L, sodium hypophosphite: 30g/L, anhydrous sodium acetate: 16/L, Trisodium Citrate: 16g/L, CNT:0.3g/L, thiocarbamide: 1g/L, with newborn acid for adjusting pH to 6 ~ 8.
6) tensio-active agent: adopt SDS:0.4g/L.
Embodiment 1:
Carbon nanotube (Carbon nano-tube, CNT, hereinafter referred to as CNT) raw material is placed in the vitriol oil and boils 6h, is finally washed till neutrality with deionized water, put into loft drier after filtration and carry out drying at 80 DEG C.
Embodiment 2:
CNT raw material is placed in concentrated nitric acid and boils 6h, be finally washed till neutrality with deionized water, put into loft drier after filtration and carry out drying at 80 DEG C.
Embodiment 3:
The vitriol oil and the concentrated nitric acid that CNT raw material are placed in volume fraction 3:1 boil 6h, are finally washed till neutrality with deionized water, put into loft drier and carry out drying after filtration at 80 DEG C.
Fig. 2 is the TEM photo of the CNT before and after embodiment 3 acid treatment.As can be seen from Fig. 2 (a), Fig. 2 (c), the CNT after peracid treatment is wound around agglomeration obviously to be reduced.Simultaneously comparison diagram 2(b), Fig. 2 (d) is not difficult to find, through overpickling oxidation, there is black group in carbon nano tube surface, after through turning out to be hydroxyl or carboxylic group.
Fig. 3 is carbon nanotube (CNT) infrared spectra picture before and after embodiment 3 acid treatment.As seen from Figure 3 no matter before concentrated acid process or after processing, the infrared spectrum of carbon nanotube there is obvious hydroxyl peak (3444cm
-1) and C=C structure absorption peak (1558cm
-1).Adsorption peak (the 1703cm of carboxyl on collection of illustrative plates before activation
-1) and not obvious, and after overpickling oxidation carbon nanotube infrared spectrum on there is obvious carboxyl peak.This shows through mixing acid-treated carbon nano tube surface not only with light base, but also has brought carboxyl functional group, which further improves activity and the wetting ability of carbon nanotube.
Embodiment 4:
1) pre-grinding process: matrix is progressively polished successively on 80 orders, 600 orders, 800 object metallographic waterproof abrasive papers, makes any surface finish;
2) alkali cleaning: the matrix through pre-grinding process is placed in alkaline wash, soak 10min, temperature is 80 DEG C;
3) pickling: the matrix through alkali cleaning is placed in pickle solution, soaks 5min, with distilled water flushing after pickling;
4) activate: the matrix through overpickling is placed in activation solution, activation 30s;
5) chemical plating solution is prepared: chemical plating solution is by single nickel salt: 28g/L, sodium hypophosphite: 30g/L, anhydrous sodium acetate: 16/L, Trisodium Citrate: 16g/L, CNT:0.3g/L(processes without embodiment 1 ~ embodiment 3), thiocarbamide: 1g/L, with the aqueous solution of newborn acid for adjusting pH to 6 ~ 8;
6) plating: the matrix after activation is placed in the chemical plating solution configured, magnetic force intermittent stirring, and temperature is 88 DEG C, plating 1.5h.
Embodiment 5:
1) ~ 5) with embodiment 4;
6) stir: the chemical plating solution configured is carried out magnetic agitation, churning time 30min;
7) plating: the matrix after activation is placed in the chemical plating solution configured, and temperature is 88 DEG C, magnetic force intermittent stirring, plating 1.5h.
Embodiment 6:
1) ~ 5) with embodiment 4;
6) shake: the chemical plating solution configured is carried out ultrasonic oscillation, concussion time 20min;
7) plating: the matrix after activation is placed in the chemical plating solution after concussion, magnetic force intermittent stirring, and temperature is 88 DEG C, plating 1.5h.
Embodiment 7:
1) ~ 5) with embodiment 4;
6) stir: the chemical plating solution configured is carried out magnetic agitation, churning time 30min;
7) shake: the chemical plating solution through magnetic agitation is carried out ultrasonic oscillation, concussion time 20min;
8) plating: matrix is placed in the chemical plating solution configured, temperature is 88 DEG C, magnetic force intermittent stirring, plating 1.5h.
Embodiment 8:
1) pre-grinding process: matrix is progressively polished successively on 80 orders, 600 orders, 800 object metallographic waterproof abrasive papers, makes any surface finish;
2) alkali cleaning: the matrix through pre-grinding process is placed in alkaline wash, soak 10min, temperature is 80 DEG C;
3) pickling: the matrix through alkali cleaning is placed in pickle solution, soaks 5min; With distilled water flushing after pickling;
4) activate: the matrix through overpickling is placed in activation solution, activation 30s;
5) chemical plating solution is prepared: chemical plating solution formula is: single nickel salt: 28g/L, sodium hypophosphite: 30g/L, anhydrous sodium acetate: 16g/L, Trisodium Citrate: 16g/L, CNT:0.3g/L(processes without embodiment 1 ~ embodiment 3), thiocarbamide: 1g/L, with newborn acid for adjusting pH to 6 ~ 8;
6) stir: the chemical plating solution configured is carried out magnetic agitation, churning time 30min;
7) disperse: in the chemical plating solution through magnetic agitation, add surfactant SDS: 0.4g/L;
8) shake: the chemical plating solution through magnetic agitation is carried out ultrasonic oscillation, concussion time 20min;
9) plating: the matrix after activation is placed in the chemical plating solution after concussion, magnetic force intermittent stirring, and temperature is 88 DEG C, plating 1.5h.
Embodiment 9:
1) ~ 6) with embodiment 8;
7) disperse: in the chemical plating solution through magnetic agitation, add tensio-active agent cetyl trimethylammonium bromide (CTAB): 0.02g/L;
8) shake: the chemical plating solution through magnetic agitation is carried out ultrasonic oscillation, concussion time 20min;
9) plating: the matrix after activation is placed in the chemical plating solution after concussion, magnetic force intermittent stirring, and temperature is 88 DEG C, plating 1.5h.
Embodiment 10:
1) ~ 6) with embodiment 8;
7) disperse: in the chemical plating solution through magnetic agitation, add surfactant polyethylene (PEG): 0.04g/L;
8) shake: the chemical plating solution through magnetic agitation is carried out ultrasonic oscillation, concussion time 20min;
9) plating: the matrix after activation is placed in the chemical plating solution after concussion, magnetic force intermittent stirring, and temperature is 88 DEG C, plating 1.5h.
Embodiment 11:
1) pre-grinding process: matrix is progressively polished successively on 80 orders, 600 orders, 800 object metallographic waterproof abrasive papers, makes any surface finish;
2) alkali cleaning: the matrix through pre-grinding process is placed in alkaline wash, soak 10min, temperature is 80 DEG C;
3) pickling: the matrix through alkali cleaning is placed in pickle solution, soaks 5min.With distilled water flushing after pickling;
4) activate: the matrix through overpickling is placed in activation solution, activation 30s;
5) carbon nanotube acid oxidase: the vitriol oil and the concentrated nitric acid that carbon nanometer tube material are placed in volume fraction 3:1 boil 6h, are finally washed till neutrality with deionized water, puts into loft drier and carry out drying at 80 DEG C after filtration;
6) chemical plating solution is prepared: chemical plating solution is by single nickel salt: 28g/L, sodium hypophosphite: 30g/L, anhydrous sodium acetate: 16g/L, Trisodium Citrate: 16g/L, CNT:0.3g/L(is through the process of previous step acid oxidase), thiocarbamide: 1g/L, with the aqueous solution of newborn acid for adjusting pH to 6 ~ 8;
7) stir: the chemical plating solution configured is carried out magnetic agitation, churning time 30min;
8) shake: the chemical plating solution through magnetic agitation is carried out ultrasonic oscillation, concussion time 20min;
9) plating: the matrix after activation is placed in the chemical plating solution after concussion, magnetic force intermittent stirring, and temperature is 88 DEG C, plating 1.5h.
Fig. 4 is CNT content (without dispersion agent in chemical plating solution) in the Ni-P-CNT nano-composite coating of embodiment 11 acquisition.
The Ni-P-CNT nano-composite coating surface topography (200 times of metallographs) that Fig. 5 (a) obtains for embodiment 11.
Fig. 9 is the Ni-P-CNT nano-composite coating hardness value (without dispersion agent in chemical plating solution) that embodiment 11 obtains.
Figure 10 is the Ni-P-CNT nano-composite coating polarization curve (in chemical plating solution surfactant-free) that embodiment 11 obtains.
Embodiment 12:
1) ~ 7) with embodiment 11;
8) disperse: in the chemical plating solution through magnetic agitation, add Surfactant SDS (SDS), the addition of sodium lauryl sulphate (SDS) is 0.4g/L;
9) shake: the chemical plating solution through magnetic agitation is carried out ultrasonic oscillation, concussion time 20min;
10) plating: the matrix after activation is placed in the chemical plating solution after concussion, magnetic force intermittent stirring, and temperature is 88 DEG C, plating 1.5h.
Fig. 4 is CNT content (dispersion agent in chemical plating solution is SDS) in the Ni-P-CNT nano-composite coating of embodiment 12 acquisition.
The Ni-P-CNT nano-composite coating surface topography (200 times of metallographs) that Fig. 5 (b) obtains for embodiment 12.
Fig. 6 is the Ni-P-CNT nano-composite coating SEM surface topography that embodiment 12 obtains.
Fig. 7 is the Ni-P-CNT nano-composite coating SEM Cross Section Morphology that embodiment 12 obtains.
Fig. 8 is that the Ni-P-CNT nano-composite coating EDS that embodiment 12 obtains can spectrogram.
Fig. 9 is the Ni-P-CNT nano-composite coating hardness value (dispersion agent in chemical plating solution is SDS) that embodiment 12 obtains.
Figure 10 is the Ni-P-CNT nano-composite coating polarization curve (dispersion agent in chemical plating solution is surfactant SDS) that embodiment 12 obtains.
The Ni-P-CNT nano-composite coating metallograph (100 times) that Figure 11 (d) obtains for embodiment 12.
Figure 12 is the polarization curve (CNT:0.3g/L) of the Ni-P-CNT nano-composite coating that embodiment 17 obtains
Figure 13 is the Ni-P-CNT nano-composite coating wear rate curve when load is 5N, 10N and 15N respectively that embodiment 12 obtains.
Figure 14 is the Ni-P-CNT nano-composite coating friction coefficient curve when load is 5N, 10N and 15N respectively that embodiment 12 obtains.
The wear shape of Ni-P-CNT nano-composite coating when load is 10N (50 times of metallographs) that Figure 15 (d) obtains for embodiment 12.
Figure 16 is the abrasion loss of Ni-P-CNT nano-composite coating when load is 10N that embodiment 12 obtains.
The wear morphology of Ni-P-CNT nano-composite coating when load is 10N (50 times, 200 times metallographs) that Figure 17 (c), (d) obtain for embodiment 12.
Embodiment 13:
1) ~ 7) with embodiment 11;
8) disperse: in the chemical plating solution through magnetic agitation, add tensio-active agent cetyl trimethylammonium bromide (CTAB), the addition of cetyl trimethylammonium bromide (CTAB) is 0.02g/L;
9) shake: the chemical plating solution through magnetic agitation is carried out ultrasonic oscillation, concussion time 20min;
10) plating: the matrix after activation is placed in the chemical plating solution after concussion, magnetic force intermittent stirring, and temperature is 88 DEG C, plating 1.5h.
Fig. 4 is CNT content (dispersion agent in chemical plating solution is cetyl trimethylammonium bromide, i.e. CTAB) in the Ni-P-CNT nano-composite coating of embodiment 13 acquisition.
The Ni-P-CNT nano-composite coating surface topography (200 times of metallographs) that Fig. 5 (c) obtains for embodiment 13.
Fig. 9 is the Ni-P-CNT nano-composite coating hardness value (dispersion agent in chemical plating solution is CTAB) that embodiment 13 obtains.
Figure 10 is the Ni-P-CNT nano-composite coating polarization curve (dispersion agent in chemical plating solution is cetyl trimethylammonium bromide, i.e. CTAB) that embodiment 13 obtains.
Embodiment 14:
1) ~ 7) with embodiment 11;
8) disperse: in the chemical plating solution through magnetic agitation, add surfactant polyethylene (PEG), the addition of polyoxyethylene glycol (PEG) is 0.04g/L;
9) shake: the chemical plating solution through magnetic agitation is carried out ultrasonic oscillation, concussion time 20min;
10) plating: the matrix after activation is placed in the chemical plating solution after concussion, magnetic force intermittent stirring, under temperature is 88 DEG C of conditions, plating 1.5h.
Fig. 4 is CNT content (dispersion agent in chemical plating solution is polyoxyethylene glycol, i.e. PEG) in the Ni-P-CNT nano-composite coating of embodiment 14 acquisition.
The Ni-P-CNT nano-composite coating surface topography (200 times of metallographs) that Fig. 5 (d) obtains for embodiment 14.
Fig. 9 is the Ni-P-CNT nano-composite coating hardness value (dispersion agent in chemical plating solution is polyoxyethylene glycol, i.e. PEG) that embodiment 14 is made.
Figure 10 is the Ni-P-CNT nano-composite coating polarization curve (dispersion agent in chemical plating solution is polyoxyethylene glycol, i.e. PEG) that embodiment 14 is made.
Embodiment 15:
1) pre-grinding process: matrix is progressively polished successively on 80 orders, 600 orders, 800 object metallographic waterproof abrasive papers, makes any surface finish;
2) alkali cleaning: the matrix through pre-grinding process is placed in alkaline wash, soak 10min, temperature is 80 DEG C;
3) pickling: the matrix through alkali cleaning is placed in pickle solution, soaks 5min.With distilled water flushing after pickling;
4) activate: the matrix through overpickling is placed in activation solution, activation 30s;
5) chemical plating fluid is prepared: chemical plating solution formula is: single nickel salt: 28g/L, sodium hypophosphite: 30g/L, anhydrous sodium acetate: 16/L, Trisodium Citrate: 16g/L, thiocarbamide: 1g/L, with newborn acid for adjusting pH to 6 ~ 8;
6) plating: the matrix through overactivation is placed in the chemical plating solution configured, temperature is 88 DEG C, plating 1.5h.
The surface topography (100 times of metallographs) of the Ni-P alloy layer that Figure 11 (a) obtains for embodiment 15.
Figure 12 is the polarization curve of the Ni-P alloy layer that embodiment 15 obtains.
Figure 13 is the Ni-P alloy layer wear rate curve when load is 5N, 10N and 15N respectively that embodiment 15 obtains.
Figure 14 is the Ni-P alloy layer friction coefficient curve when load is 5N, 10N and 15N respectively that embodiment 15 obtains.
The wear shape of Ni-P alloy layer when load is 10N (50 times of metallographs) that Figure 15 (a) obtains for embodiment 15.
Figure 16 is the abrasion loss of Ni-P alloy layer when load is 10N that embodiment 15 obtains.
Figure 17 (a) and (b) are the wear morphology of Ni-P alloy layer when load is 10N (50 times, 200 times metallographs) that embodiment 15 obtains.
Embodiment 16:
1) pre-grinding process: matrix is progressively polished successively on 80 orders, 600 orders, 800 object metallographic waterproof abrasive papers, makes any surface finish;
2) alkali cleaning: the matrix through pre-grinding process is placed in alkaline wash, soak 10min, temperature is 80 DEG C;
3) pickling: the matrix through alkali cleaning is placed in pickle solution, soaks 5min.With distilled water flushing after pickling;
4) activate: the matrix through overpickling is placed in activation solution, activation 30s;
5) CNT acid oxidase: the vitriol oil and the concentrated nitric acid that CNT raw material are placed in volume fraction 3:1 boil 6h, are finally washed till neutrality with deionized water, put into loft drier and carry out drying after filtration at 80 DEG C;
6) chemical plating solution is prepared: chemical plating solution formula is: single nickel salt: 28g/L, sodium hypophosphite: 30g/L, anhydrous sodium acetate: 16/L, Trisodium Citrate: 16g/L, CNT:0.1g/L(is through the acid oxidase process of previous step), thiocarbamide: 1g/L, with newborn acid for adjusting pH to 6 ~ 8;
7) stir: the chemical plating solution configured is carried out magnetic agitation, churning time 30min;
8) disperse: in the chemical plating solution through magnetic agitation, add surfactant SDS: 0.4g/L;
9) shake: the chemical plating solution through magnetic agitation is carried out ultrasonic oscillation, concussion time 20min;
10) plating: the matrix after activation is placed in the chemical plating solution after concussion, magnetic force intermittent stirring, and temperature is 88 DEG C, plating 1.5h.
The surface topography (100 times of metallographs) of the Ni-P-CNT nano-composite coating that Figure 11 (b) obtains for embodiment 16.
Figure 12 is the polarization curve (CNT:0.1g/L) of the Ni-P-CNT nano-composite coating that embodiment 16 obtains.
Figure 13 is the Ni-P-CNT nano-composite coating wear rate curve when load is 5N, 10N and 15N respectively that embodiment 16 obtains.
Figure 14 is the Ni-P-CNT nano-composite coating friction coefficient curve when load is 5N, 10N and 15N respectively that embodiment 16 obtains.
The wear shape of Ni-P-CNT nano-composite coating when load is 10N (50 times of metallographs) that Figure 15 (b) obtains for embodiment 16.
Embodiment 17:
1) ~ 5) with embodiment 16;
6) chemical plating solution is prepared: chemical plating solution formula is by single nickel salt: 28g/L, sodium hypophosphite: 30g/L, anhydrous sodium acetate: 16/L, Trisodium Citrate: 16g/L, CNT:0.2g/L(is through the acid oxidase process of previous step), thiocarbamide: 1g/L, with the aqueous solution of newborn acid for adjusting pH to 6 ~ 8;
7) stir: the chemical plating solution configured is carried out magnetic agitation, churning time 30min;
8) disperse: in the chemical plating solution through magnetic agitation, add surfactant SDS: 0.4g/L;
9) shake: the chemical plating solution through magnetic agitation is carried out ultrasonic oscillation, concussion time 20min;
10) plating: the matrix after activation is placed in the chemical plating solution after concussion, magnetic force intermittent stirring, and temperature is 88 DEG C, plating 1.5h.
The surface topography (100 times of metallographs) of the Ni-P-CNT nano-composite coating that Figure 11 (c) obtains for embodiment 17.
Figure 12 is the polarization curve (CNT:0.2g/L) of the Ni-P-CNT nano-composite coating that embodiment 17 obtains.
Figure 13 is the Ni-P-CNT nano-composite coating wear rate curve when load is 5N, 10N and 15N respectively that embodiment 17 obtains.
Figure 14 is the Ni-P-CNT nano-composite coating friction coefficient curve when load is 5N, 10N and 15N respectively that embodiment 17 obtains.
The wear shape of Ni-P-CNT nano-composite coating when load is 10N (50 times of metallographs) that Figure 15 (c) obtains for embodiment 17.
Embodiment 18:
1) ~ 5) with embodiment 16;
6) chemical plating solution is prepared: chemical plating solution formula is: single nickel salt: 28g/L, sodium hypophosphite: 30g/L, anhydrous sodium acetate: 16/L, Trisodium Citrate: 16g/L, CNT:0.4g/L(is through the acid oxidase process of previous step), thiocarbamide: 1g/L, with newborn acid for adjusting pH to 6 ~ 8;
7) stir: the chemical plating solution configured is carried out magnetic agitation, churning time 30min;
8) disperse: in the chemical plating solution through magnetic agitation, add surfactant SDS: 0.4g/L;
9) shake: the chemical plating solution through magnetic agitation is carried out ultrasonic oscillation, concussion time 20min;
10) plating: the matrix after activation is placed in the chemical plating solution after concussion, magnetic force intermittent stirring, and temperature is 88 DEG C, plating 1.5h.
The surface topography (100 times of metallographs) of the Ni-P-CNT nano-composite coating that Figure 11 (e) obtains for embodiment 18.
Figure 12 is the polarization curve (CNT:0.4g/L) of the Ni-P-CNT nano-composite coating that embodiment 18 obtains.
Figure 13 is the Ni-P-CNT nano-composite coating wear rate curve when load is 5N, 10N and 15N respectively that embodiment 18 obtains.
Figure 14 is the Ni-P-CNT nano-composite coating friction coefficient curve when load is 5N, 10N and 15N respectively that embodiment 18 obtains.
The wear shape of Ni-P-CNT nano-composite coating when load is 10N (50 times of metallographs) that Figure 15 (e) obtains for embodiment 18.
Embodiment 19:
1) ~ 5) with embodiment 16;
6) chemical plating solution is prepared: chemical plating solution formula is: single nickel salt: 28g/L, sodium hypophosphite: 30g/L, anhydrous sodium acetate: 16g/L, Trisodium Citrate: 16g/L, CNT:0.5g/L(is through the acid oxidase process of previous step), thiocarbamide: 1g/L, with newborn acid for adjusting pH to 6 ~ 8;
7) stir: the chemical plating solution configured is carried out magnetic agitation, churning time 30min;
8) disperse: in the chemical plating solution through magnetic agitation, add surfactant SDS: 0.4g/L;
9) shake: the chemical plating solution through magnetic agitation is carried out ultrasonic oscillation, concussion time 20min;
10) plating: the matrix after activation is placed in the chemical plating solution after concussion, magnetic force intermittent stirring, and temperature is 88 DEG C, plating 1.5h.
The surface topography (100 times of metallographs) of the Ni-P-CNT nano-composite coating that Figure 11 (f) obtains for embodiment 19.
Figure 12 is the polarization curve (CNT:0.5g/L) of the Ni-P-CNT nano-composite coating that embodiment 19 obtains.
Figure 13 is the Ni-P-CNT nano-composite coating wear rate curve when load is 5N, 10N and 15N respectively that embodiment 19 obtains.
Figure 14 is the Ni-P-CNT nano-composite coating friction coefficient curve when load is 5N, 10N and 15N respectively that embodiment 19 obtains.
The wear shape of Ni-P-CNT nano-composite coating when load is 10N (50 times of metallographs) that Figure 15 (f) obtains for embodiment 19.
Embodiment 20:
1) ~ 5) with embodiment 16;
6) chemical plating solution is prepared:
Chemical plating solution formula is: single nickel salt: 28g/L, sodium hypophosphite: 30g/L, anhydrous sodium acetate: 16/L, Trisodium Citrate: 16g/L, SiC:0.3g/L, thiocarbamide: 1g/L, with newborn acid for adjusting pH to 6 ~ 8;
7) stir: the chemical plating solution configured is carried out magnetic agitation, churning time 30min;
8) shake: the chemical plating solution through magnetic agitation is carried out ultrasonic oscillation, concussion time 20min;
9) plating: the matrix after activation is placed in the chemical plating solution after concussion, magnetic force intermittent stirring, and temperature is 88 DEG C, and plating time is 1.5h.
Ni-P-SiC in Figure 16 is the abrasion loss of Ni-P-SiC composite deposite when load is 10N that embodiment 20 obtains.
The wear morphology of Ni-P-SiC composite deposite when load is 10N (50 times, 200 times metallographs) that Figure 17 (e), (f) obtain for embodiment 20.
Claims (1)
1. a preparation method for Ni-P-CNT compound coating, is characterized in that, concrete preparation process is as follows:
Step one, carries out pre-grinding process by matrix, makes any surface finish;
Step 2, is placed in alkaline wash by the matrix after pre-grinding process, and soak 10min, temperature is 80 DEG C, and described alkaline wash is by sodium hydroxide: 50g/L, sodium carbonate: 5g/L, tertiary sodium phosphate: 25g/L, the aqueous solution that water glass 13g/L is formulated;
Step 3, is placed in pickle solution by the matrix after alkali cleaning and soaks 5min, with distilled water flushing after pickling, described pickle solution to be concentration be 10% sulphuric acid soln;
Step 4, is placed in activation solution by matrix through the matrix of overpickling and activates 30s, described activation solution to be concentration be 4% hydrochloric acid soln;
Step 5, carbon nanotube is carried out acid oxidase process, the method of described acid oxidase process is: the vitriol oil and the concentrated nitric acid that carbon nanometer tube material are placed in volume fraction 3:1 boil 6h, are finally washed till neutrality with deionized water, puts into loft drier and carry out drying after filtration at 80 DEG C;
Step 6, preparation chemical plating solution, described chemical plating solution is by single nickel salt: 28g/L, inferior sodium phosphate: 30g/L, anhydrous sodium acetate: 16g/L, Trisodium Citrate: 16g/L, carbon nanotube: 0.1g/L ~ 0.5g/L, tensio-active agent: 0.4g/L, thiocarbamide: 1g/L, with the aqueous solution of lactic acid adjust ph 6 ~ 8;
Step 7, carries out magnetic agitation by the chemical plating solution configured; And in chemical plating solution, add the tensio-active agent of 0.3g/L; And carry out ultrasonic oscillation;
Step 8, is placed in chemical plating solution by the matrix through overactivation, magnetic force intermittent stirring, and under temperature is 88 DEG C of conditions, plating 1.5h, namely obtains Ni-P-CNT compound coating on matrix surface;
The described magnetic agitation time is 30min;
Described tensio-active agent selects sodium lauryl sulphate or cetyl trimethylammonium bromide or polyoxyethylene glycol.
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| JP6531277B2 (en) * | 2015-03-30 | 2019-06-19 | 株式会社 コーア | Electroless plating solution and electroless plating method |
| CN108456835B (en) * | 2017-02-21 | 2020-04-07 | 南京理工大学 | Carbon nano tube reinforced nickel-based composite material and preparation method thereof |
| CN108165958A (en) * | 2018-01-25 | 2018-06-15 | 广东工业大学 | A kind of method of red copper surface chemical Ni-P plating-graphene composite deposite |
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